A variety of art is available that describes various salts and methods of making them.
U.S. Pat. No. 4,331,609 to Orr teaches an antiperspirant active comprising aluminum and zirconium made with separate aluminum and zirconium compounds as well as a neutral amino acid wherein the molar ratio of neutral amino acid to total metal is from about 0.90 to about 0.24. The total metal:chlorine ratio in the complex that is formed is less than 1.30.
EP publication number 0 047 650 describes aqueous solution-stable antiperspirant complexes comprising an aluminum compound, a zirconium or hafnium compound, a water soluble neutral amino acid and an inorganic acid. The molar ratio of neutral amino acid to total metal is from about 0.90 to about 0.24 in an aqueous system, and the molar ratio of neutral amino acid to total metal is from about 0.90 to about 0.75 in a non-aqueous system. The total metal:chlorine ratio in the complex that is formed is less than 1.30.
United Kingdom Patent Application GB 2,076,289 describes an antiperspirant compositions comprising a combination of an aluminum chloride and an aluminum zirconium hydroxychloride in a synergistic mixture. The metal:chloride ratio is less than 0.9.
Canadian Patent 1,153,313 describes an antiperspirant composition which contains a buffering agent such as glycine with a synergistic mixture of aluminum chlorohydrate, aluminum chloride or aluminum zirconium polychlorohydrate complex. The molar ratio of aluminum to chloride is in the range of 0.78:1 to abut 1.95:1. Various salts are described which have a metal:halide ratio of 2.1:1-0.9:1. The glycine:zirconium ratio is much less than 1:1.
U.S. Pat. No. 4,871,525 to Giovanniello et al describes a solid powder of aluminum zirconium hydroxyl halide glycinate complex having improved antiperspirant activity wherein the glycine is used to prevent gel formation. The ratio of Zr to glycine is less than 1:1.
U.S. Pat. No. 6,126,928 to Swaile describes antiperspirant compositions wherein the molar ratio of neutral amino acid to total metal (aluminum+zirconium) is from about 0.90 to about 0.24, and the mole ratio of (aluminum+zirconium):chlorine is less than about 1.30:1.
U.S. Pat. No. 6,066,314 to Tang describes the use of post added glycine to aluminum zirconium salts in an amount in the range of 1:1.2-1:5 of zirconium:amino acid on a weight:weight basis.
None of the above cases described the combination of metal to chloride in combination with the Betaine (as defined herein) to zirconium ratio as found in the instant invention. Thus, it is surprising that the antiperspirant actives described in this invention provide more efficacious cosmetic products.
The term “betaine” is used in a variety of ways. In particular, a variety of uses of betaines with long chains can be found in the surfactant art. Such betaines may be represented by the following Formula A where n>0: The methyl groups can be replaced with other longer chain alkyls and can be straight chain or branched.
The Betaine (defined below) of this invention, however, is not a surfactant and has been found to have properties important to the field of antiperspirant salts that contain zirconium. The Betaine used in this invention is a natural product found in a number of plants in the Chenopodiaceae family, and also in fish and selected legumes. Extracted most often from sugar beets (Beta Vulgaris), it is reported as an extremely versatile molecule with a wide range of applications: food supplement, anti-irritant, skin moisturizer, skin-softening agent, skin-conditioning agent, promoter of wound healing and component in cosmetic compositions for skin aging and stressed skin.
Betaine in IUPAC nomenclature is 1-carboxy-N,N,N-trimethylmethanaminium hydroxide-inner salt, with alternative names including carboxymethyl-trimethyl-ammonium betaine or (carboxymethyl)trimethylammonium hydroxide-inner salt or glycine betaine or glycoll betaine or glycyl betaine or trimethyl glycine or trimethylglycoll. For convenience here the material of Formula I (C5H11NO2; Mass=117.08 amu; molecular weight=117.15; analysis as C: 51.26; H: 9.46; N: 11.96; O: 27.32) will be referred to as Betaine. 
The hydrochloride form is also included in the scope of this invention. The hydrochloride form may be represented by Formula IA: 
Betaine appears in numerous patents, with a wide range of applications.
Note that for purposes of this application, the term “betaine” will be used if any compound of Formula A is described. The term “Betaine” will be used if a compound of Formula I is described. The term “Betaine hydrochloride” will be used if a compound of Formula IA is described.
PCT Publication WO 00/67726 describes host-guest processes and formulations containing Betaine for delivering bio-affecting compounds and topical compositions for cosmetic or pharmaceutical uses formed by the processes. The processes comprise mixing, in any order: (i) a nonionic surfactant; (ii) an amphoteric surfactant; (iii) a solvent for the amphoteric surfactant; (iv) an aromatic compound; (v) an aluminum cation; (vi) a Lewis acid that is not a Bronsted-Lowry acid; and (vii) a Bronsted-Lowry acid.
U.S. Pat. No. 5,877,143 describes a composition containing a lamellar liquid crystalline phase which comprises betaines and amine oxides. This is a pumpable, fluid composition of amine oxide, betaine and/or sultaine is prepared with active concentration of about 36-45% of these materials by the addition of alkaline earth or aluminum salts.
German Patent DE 19725087 is related to cosmetic and dermatologic oil-in-water emulsion formulations for light protection containing hydrophobic inorganic micropigments and hydrophilic surfactants.
PCT Publication WO 97/23594 describes skin cleansing compositions with enhanced antimicrobial activity comprising 0.1-30% of an amphoteric, zwitterionic, nonionic, anionic and/or cationic emulsifier, 0.00001-5% of a Ag compound (AgCl, Ag2CO3, etc.), deposited on a particulate inert support material (metal oxides, especially TiO2) as antimicrobial agent, and H2O. A typical composition contains cetyl betaine.
Japanese Patent JP 52093633 describes chemical polishing solutions for aluminum and its alloys. Al or its alloys are chemically polished in a H3PO4—H2SO4 solution containing a betaine and organic polythio sulfonic acid salt.
British Patent GB 2354771 relates to bactericide combinations in detergents. The detergent comprises a bactericide in combination with an anionic, cationic, nonionic or amphoteric surfactant which has a C12-18 alkyl group as the longest chain attached to the hydrophilic moiety.
Japanese Patent JP 2001163752 describes long-lasting cosmetic makeup compositions comprising plate-type glossy polymer powders and antiperspirants.
European Patent EP 1005853 describes the use of betaines as antiperspirants. Mono-, di-, and trimethylammonio-substituted carboxylic acids (R1)(R2)(R3)N+—(CH2)nC(O)O— (with R1-R3═H, Me; n=1-10) are active as antiperspirants and are compatible with the skin and with other conventional constituents of antiperspirant and deodorant compositions.
European Patent EP 1005852 describes the use of functionally substituted betaines as antiperspirants. Mono-, di-, and trimethylammonio-substituted carboxylic acids R1R2R3N+(CH2)nCHX(CH2)mC(O)O— and/or X(CH2)nCH(N+R1R2R3)(CH2)mC(O)O— (R1-R3=H, Me; m, n=1-8 are active as antiperspirants and are compatible with the skin and with other conventional constituents of antiperspirant and deodorant compositions.
Japanese Patent JP 11130652 discloses skin-conditioning and moisturizing cosmetics containing clay minerals and low-molecular-weight betaines to inhibit the release of pyrrolidonecarboxylic acid (a natural moisturizing factor) from human skin.
German Patent DE 2610225 describes aluminum salts of Betaine chloride being useful as ulcer inhibitors, for treatment of gastritis, to promote wound healing, and as antiperspirants and deodorants.
PCT Publication WO 01/62222 describes cosmetic compositions containing phospholipids and quaternary amines. The invention relates to a cosmetic composition, especially for use on aging and/or stressed skin, the composition comprising, in addition to water, at least one substance that forms lamellar structures with water. Compositions including Betaine are described.
PCT Publication WO 01/47479 assigned to the same owner as this case describes cosmetic moisturizing compositions containing quaternary ammonium compounds. Compositions with cocamidopropyl betaine are described.
PCT Publication WO 01/39730 describes a cosmetic composition containing peat and Betaine.
PCT Publication WO 97/46246 is related to complex preparations for topical use containing Betaine to stimulate cellular and physiological processes.
PCT Publication WO 91/18588 presents a method of reducing the irritating properties of a cosmetic composition by addition of Betaine derivatives.
Japanese Patent JP 03033266 describes modified fabrics coated with a mixture of dodecyl betaine and other ingredients for controlling pH change in skin during sweating.